Abstract
The black phase of formamidinium lead iodide (FAPbI3) perovskite shows huge promise as an efficient photovoltaic, but it is not favoured energetically at room temperature, meaning that the undesirable yellow phases are always present alongside it during crystallization1,2,3,4. This problem has made it difficult to formulate the fast crystallization process of perovskite and develop guidelines governing the formation of black-phase FAPbI3 (refs. 5,6). Here we use in situ monitoring of the perovskite crystallization process to report an oriented nucleation mechanism that can help to avoid the presence of undesirable phases and improve the performance of photovoltaic devices in different film-processing scenarios. The resulting device has a demonstrated power-conversion efficiency of 25.4% (certified 25.0%) and the module, which has an area of 27.83 cm2, has achieved an impressive certified aperture efficiency of 21.4%.
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Data availability
The data that support the findings of this study are available from the corresponding authors upon reasonable request.
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Acknowledgements
We thank X. Miao, L. Liu, T. Zhou from Instrumentation and Service Center for Physical Sciences, and X. Lu and Z. Chen from Instrumentation Service Center for Molecular Sciences, Westlake University for help with characterizations and S. Yuan from Zhejiang University for discussions about the crystallization of perovskites. J.Xue. and R.W. acknowledge a grant from the Natural Science Foundation of Zhejiang Province of China (LD22E020002). J.Xue. acknowledges grants from the National Natural Science Foundation of China (62274146), the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering (2021SZ-FR006) and the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (61721005). R.W. acknowledges funding from Westlake University. M.K.N. and P.J.D. thank the Valais Energy Demonstrators fund. This work was also supported by the National Natural Science Foundation of China (62204209). We used the resources of the Advanced Light Source and the US Department of Energy Office of Science User Facility (contract DE-AC02-05CH11231), beamline 12.3.2 and the in situ spin coater. Work at the Molecular Foundry was supported by the Office of Science and Office of Basic Energy Sciences of the US Department of Energy (contract DE-AC02-05CH11231) T.K. thanks the German Research Foundation (DFG) for funding (KO6414). Computing resources used in this work were provided by the National Center for High Performance Computing of Turkey (UHeM).
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J.Xue., R.W. and P.S. conceived the idea. P.S. did the two-step fabrication of perovskite films and devices, and performed the data analysis under the supervision of J.Xue. and R.W. Y.D. and B.D. did the one-step fabrication of the small-area perovskite devices and fabricated the modules under the supervision of M.K.N. Q.X. and S.T. did the in situ characterizations under the supervision of Y.Y. and C.M.S.-F. C.M.S.-F., J.L.S. and T.K. designed the in situ photoluminescence, the in situ multimodal diffraction monitoring system and facilitated the in situ measurements. I.Y. and C.Y. did the theoretical calculations. W.F., J.Xu., Y.T., D.G., X.Z., K.Z. and L.Y. assisted with the characterizations and device fabrication. P.J.D. and D.Y. provided discussions. J.Xue. wrote the manuscript. All the authors discussed the results and commented on the manuscript.
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Extended data figures and tables
Extended Data Fig. 1 FTIR measurements for investigating the interaction between PAd and Pb-I framework.
FTIR spectra of PAd, PbI2 and PAd mixed with PbI2.
Extended Data Fig. 2 DFT slabs of FA-based perovskite lattice with different surface termination.
The slab of a, bare FA-based perovskite and the ones terminated with b, PRd, c, BAd, d, PAd, and the surface energies of the (100) planes.
Extended Data Fig. 3 In-situ GIXRD patterns of perovskite films.
In-situ GIXRD patterns of a, the control perovskite film and the ones fabricated with b, PRd, c, BAd, d, PAd.
Extended Data Fig. 4 Evolutions of the azimuth angles during the nucleation stage of perovskite films.
Evolution of the azimuth angle during the nucleation of a, the control perovskite film and the films fabricated with b, PRd, c, BAd and d, PAd.
Extended Data Fig. 5 In-situ GIXRD monitoring of the initial nucleation stage of perovskite films.
In-situ GIXRD monitoring of the initial nucleation stage of perovskite films fabricated a, with and b, without PAd. The control perovskite nuclei contained a diffraction peak at around 14°, whereas the one with PAd showed a diffraction peak at around 14.4°, indicating compressive strain within the lattice of the perovskite nuclei.
Extended Data Fig. 6 Evolution of the PL spectra during the perovskite nucleation stage.
Evolution of the PL spectra during the nucleation stage of a, the control perovskite film and the ones with b, PRd, c, BAd and d, PAd.
Extended Data Fig. 7 Optical properties of perovskite films.
a, TRPL plots of the perovskite film with PAd and the control. The PL lifetime was fitted to be 4.89 μs and 0.5 μs for the perovskite film with PAd and the control, respectively. b, PL spectra of the perovskite film with PAd and the control. The above-mentioned perovskite films were deposited by two-step method on glass substrates for measurements.
Extended Data Fig. 8 Photovoltaic parameters of perovskite devices made by two-step method.
Box plots showing the distribution of the a, PCE, b, FF, c, Voc, and d, Jsc for the control and the PAd devices made by two-step method. Centre line, median; box limits, 25th and 75th percentiles; curve, normal distribution curve; whiskers, outliers.
Extended Data Fig. 9 Photovoltaic parameters of perovskite devices made by one-step method.
Box plots showing the distribution of the a, FF, b, Voc, and c, Jsc for the control and PAd devices made by one-step method. Centre line, median; box limits, 25th and 75th percentiles; curve, normal distribution curve; whiskers, outliers.
Extended Data Fig. 10 Photovoltaic parameters of perovskite modules.
Box plots showing the distribution of the a, PCE, b, FF, c, Voc, d, Isc for the control and the PAd-based perovskite modules with an aperture area of 30.86 cm2. Centre line, median; box limits, 25th and 75th percentiles; curve, normal distribution curve; whiskers, outliers. In this case, the width of P2 lines and P3 lines was 200 μm and 100 μm respectively and the geometric fill factor (GFF) is around 0.90.
Supplementary information
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This file contains Supplementary Notes 1–4, Supplementary Figs. 1–25, Supplementary Tables 1–3 and references.
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Shi, P., Ding, Y., Ding, B. et al. Oriented nucleation in formamidinium perovskite for photovoltaics. Nature 620, 323–327 (2023). https://doi.org/10.1038/s41586-023-06208-z
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DOI: https://doi.org/10.1038/s41586-023-06208-z
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